14307-99-4Relevant articles and documents
Electrochemical Tandem Olefination and Hydrogenation Reaction with Ammonia
Zhang, Xiaofeng,Jiang, Runze,Cheng, Xu
, p. 16016 - 16025 (2021/08/24)
An electrochemical Horner-Wadsworth-Emmons/hydrogenation tandem reaction was achieved using ammonia as electron and proton donors. The reaction could give two-carbon-elongated ester and nitrile from aldehyde or ketones directly. This reaction could proceed with a catalytic amount of base or even without a base. The ammonia provides both the electron and proton for this tandem reaction and enables the catalyst-free hydrogenation of an α,β-unsaturated HWE intermediate. More than 40 examples were reported, and functional groups, including heterocycles and hydroxyl, were tolerated.
Carbonyls as Latent Alkyl Carbanions for Conjugate Additions
Dai, Xi-Jie,Wang, Haining,Li, Chao-Jun
supporting information, p. 6302 - 6306 (2017/05/19)
Conjugate addition of carbon nucleophiles to electron-deficient olefins is one of the most powerful methods for forming carbon–carbon bonds. Despite great achievements in controlling the selectivity, variation of the carbon nucleophiles remains largely underexplored, with this approach relying mostly on organometallic reagents. Herein, we report that naturally abundant carbonyls can act as latent carbon nucleophiles for conjugate additions through a ruthenium-catalyzed process, with water and nitrogen as innocuous byproducts. The key to our success is homogeneous ruthenium(II) catalysis, combined with phosphines as spectator ligands and hydrazine as the reducing agent. This chemistry allows the incorporation of highly functionalized alkyl fragments into a vast array of electron-deficient olefins under mild reaction conditions in a reaction complementary to the classical organometallic-reagent-based conjugate additions mediated or catalyzed by “soft” transition metals.
Umpolung synthesis of branched α-functionalized amines from imines via photocatalytic three-component reductive coupling reactions
Fuentes De Arriba, Angel L.,Urbitsch, Felix,Dixon, Darren J.
, p. 14434 - 14437 (2016/12/23)
A three component reductive coupling reaction of a (hetero)aromatic amine, a (hetero)aromatic aldehyde and an electron deficient olefin catalysed by eosin Y under green LED light irradiation, for the direct generation of γ-amino acid derivatives, is described. This new umpolung synthesis of amines, which exploits the high nucleophilicity of a putative α-amino radical intermediate, generated via single electron reduction of the in situ generated imine from the Hantzsch ester terminal reductant, is efficient, operationally simple, broad in scope and offers a complementary strategy to existing synthetic approaches.
